Acetoacetic arylide azo dyestuffs for synthetic materials, especially polyester

ABSTRACT

Dyestuffs of the formula ##STR1## wherein R denotes hydrogen or alkyl, 
     X denotes R, Cl or Br, 
     m and p denotes 0 or 1, 
     n denotes 2 to 4, 
     A denotes oxygen or --NR-- and 
     B denotes C 1  -C 8  -alkyl, alkenyl, cycloalkyl, aralkyl or aryl, 
     are especially suitable for the dyeing of polyester-materials; they give deep yellow dyeings with good light fastness properties.

This is a division of application Ser. No. 093.947, filed Nov. 14, 1979 now abandoned.

The invention relates to new azo disperse dyestuffs, processes for their preparation and their use for dyeing hydrophobic synthetic materials.

In one of their possible tautomeric forms, the dyestuffs, which are free from sulphonic acid groups and ammonium groups, correspond to the formula (I) ##STR2## wherein R denotes hydrogen or C₁ -C₄ -alkyl,

X denotes R, Cl or Br,

m denotes the number 0 or 1,

n denotes a number from 2 to 4,

p denotes the number 0 or 1,

A denotes oxygen or --NR-- and

B denotes optionally substituted C₁ -C₈ -alkyl, alkenyl, cycloalkyl, aralkyl or aryl.

Suitable radicals R are, besides hydrogen, CH₃ and C₂ H₅, linear or branched C₃ - and C₄ -alkyl radicals.

The straight-chain or branched alkyl radicals B have 1-8 C atoms and can be monosubstituted, for example, by CN, Cl, Br, C₁ -C₄ -alkoxy, phenoxy or R--(OC₂ H₄)_(r) --, r denoting a number from 2 to 4.

The preferred alkenyl radical B is the allyl radical.

Suitable cycloalkyl radicals B are cyclohexyl or cyclopentyl radicals, which can be substituted, for example by methyl.

A suitable aralkyl radical B is the benzyl, phenylethyl or phenylpropyl radical.

A suitable aryl radical B is phenyl, which can be substituted by NO₂ or mono-, di- or tri-substituted by CH₃, OCH₃, OC₂ H₅ or CF₃, or 1-naphthyl.

Preferred dyestuffs are those of the formula (II) ##STR3## wherein R' denotes hydrogen, CH₃ or C₂ H₅,

X' denotes R' or Cl,

A' denotes oxygen or --NH--,

B' denotes C₁ -C₈ -alkyl which is optionally substituted by C₁ -C₄ -alkoxy, phenoxy, Cl or R--(OC₂ H₄)_(r) --, or phenyl, tolyl, benzyl or 1-naphthyl and

m, p, R and r have the abovementioned meaning.

Those dyestuffs of the formula (II) in which

m represents the number 0,

R' represents H,

X' represents CH₃ and

B' represents C₁ -C₈ -alkyl are particularly preferred.

Bulky radicals, such as, for example, t-butyl, are preferably in those positions where they cause no steric hindrance.

The new dyestuffs of the formula (I) are obtained either by a procedure in which an amine of the general formula (III) ##STR4## is diazotised and the diazotisation product is coupled with an acetoacetic acid arylide of the general formula (IV) ##STR5## wherein X, R, A, B, m, n and p have the abovementioned meaning,

or by a procedure in which an azo dyestuff of the general formula (V) ##STR6## is reacted with an acylating agent of the general formula (VI) or (VII) ##STR7## wherein Z represents halogen, preferably chlorine, and

A, B and p have the abovementioned meaning,

or by a procedure in which an azo dyestuff of the general formula (VIII) ##STR8## is alkylated with an alkylating agent of the general formula (IX)

    L--B"                                                      (IX)

wherein

B" denotes C₁ -C₈ -alkyl, alkenyl, cycloalkyl or aralkyl, optionally substituted by C₁ -C₄ -alkoxy, phenoxy, Cl or R--(OC₂ H₄)_(r) --, and

L denotes a leaving group, such as, for example, Cl, Br, I, OSO₂ -phenyl, OSO₂ -tolyl or OSO₂ OB".

Some of the coupling components of the general formula (IV) are known, or they are obtained by processes which are known from the literature, either by a procedure in which an amine of the general formula (X) ##STR9## is reacted with ethyl acetoacetate or diketene, or by a procedure in which an acetoacetic arylide of the general formula (XI) ##STR10## is acylated with the acylating agent (VI) or (VII) (m=1) or is alkylated with the alkylating agents (IX) (m=0).

The reaction of the dyestuffs (V) or of the acetoacetic arylides (XI), m=1, with the acylating agents (VI) or (VII) is preferably carried out in organic solvents which are inert towards (VI)/(VII), such as, for example, acetone, methyl ethyl ketone, cyclohexanone, CH₃ -CN, toluene, chlorobenzene, dichlorobenzene or nitrobenzene, acid-binding agents, such as, for example, Na carbonate or Ca carbonate, MgO, trialkylamine or pyridine, being added if appropriate.

The dyestuffs (VIII) or the acetoacetic arylides (XI), m=0, are alkylated with the compounds (IX) in the solvents customary for alkylation reactions, acid-binding agents being added if appropriate.

The dyestuffs according to the invention, especially in the finely dispersed form, are suitable for dyeing and printing articles consisting of synthetic materials, such as, for example, polyolefines, polyvinyl compounds, cellulose 21/2-acetate, cellulose triacetate and, in particular, polyester materials, for example polyethylene glycol terephthalate, or analogous polymers. When applied to these materials by the customary dyeing and printing processes, they give deep yellow dyeings and prints with good fastness properties, in particular good fastness to light.

In the examples which follow, "parts" denote parts by weight.

EXAMPLE 1

15.2 parts of 2-nitro-4-methylaniline are diazotised in 80 parts of water and 20 parts of concentrated HCl, at 0°-3° C., after adding 100 parts of ice, by adding one equivalent of 30% strength NaNo₂ solution dropwise. A little amidosulphonic acid is then added and, if necessary, the solution is clarified by adding 10 parts of kieselguhr.

This solution is allowed to run into a suspension, precooled to 3°-5° C., of 24.9 parts of N-(4-butoxyphenyl)-3-oxobutyramide in about 300 parts of water, during which the pH value is kept at 5 by adding 40% strength sodium hydroxide solution dropwise, and the mixture is stirred for 3-4 hours. After filtering off the product, washing it with water and drying it, about 39 parts (95% of theory) of the dyestuff of the formula ##STR11## which dyes polyester materials, for example, in yellow shades with outstanding fastness properties, are obtained.

EXAMPLE 2

The diazotisation product obtained from 15.2 parts of 2-nitro-4-methylaniline is coupled with 23.7 parts of N-(4-β-hydroxyethyloxyphenyl)-3-oxo-butyramide, by the process described in Example 1.

After drying the product, about 38 parts (95% of theory) of the dyestuff ##STR12## are obtained.

EXAMPLE 2a

40 parts of the dyestuff prepared according to Example 2 are heated to 110°-120° C. in about 200 parts of chlorobenzene with 10 parts of n-butylisocyanate for 4-5 hours. After this time, according to the thin layer chromatogram, the reaction has ended. After cooling the mixture, filtering off the product, washing it with methanol and drying it, about 45 parts of the dyestuff of the formula ##STR13## which dyes polyester materials, for example, in yellow shades with outstanding fastness properties, are obtained.

The yellow dyestuffs listed in the following tables serve to illustrate the present invention.

                  TABLE 1                                                          ______________________________________                                          ##STR14##                                                                     Example                                                                        No.      R          X        B                                                 ______________________________________                                         3        H          H        CH.sub.3                                          4        H          H        C.sub.2 H.sub.5                                   5        H          H        CH.sub.3OC.sub.2 H.sub.4                          6        H          H        C.sub.4 H.sub.9                                   7        H          H        C.sub.6 H.sub.13                                  8        H          H        CH.sub.3(OC.sub.2 H.sub.4).sub.2                  9        H          CH.sub.3 CH.sub.3                                          10       H          CH.sub.3 C.sub.2 H.sub.5                                   11       H          CH.sub.3 i-C.sub.3 H.sub.7                                 12       H          CH.sub.3 i-C.sub.4 H.sub.9                                 13       H          CH.sub.3 C.sub.6 H.sub.13                                  14       H          CH.sub.3 CH.sub.3OC.sub.2 H.sub.4                          15       H          CH.sub.3 CH.sub.3(OC.sub.2 H.sub.4).sub.2                  16       H          CH.sub.3 CH.sub.3(OC.sub.2 H.sub.4).sub.3                  17       H          C.sub.2 H.sub.5                                                                         CH.sub.2C.sub.6 H.sub.5                           18       H          C.sub.2 H.sub.5                                                                         C.sub.4 H.sub. 9                                  19       H          C.sub.2 H.sub.5                                                                         CH.sub.3OC.sub.2 H.sub.4                          20       H          C.sub.4 H.sub.9                                                                         CH.sub.3                                          21       H          CH.sub.3 C.sub.6 H.sub.5                                   22       H          C.sub.2 H.sub.5                                                                         C.sub.6 H.sub.5                                   23       H          i-C.sub.3 H.sub.7                                                                       C.sub.6 H.sub.5                                   24       H          CH.sub.3 CH.sub.2CHCH.sub.2                                25       H          C.sub.2 H.sub.5                                                                         CH.sub.2C.sub.6 H.sub.5                           26       2-CH.sub.3 CH.sub.3 C.sub.2 H.sub.5                                   27       2-CH.sub.3 CH.sub.3 C.sub.4 H.sub.9                                   28       2-CH.sub.3 CH.sub.3 CH.sub.2C.sub.6 H.sub.5                           29       H          Cl       CH.sub.3                                          30       H          Cl       C.sub.2 H.sub.5                                   31       H          Cl       C.sub.4 H.sub.9                                   32       H          Br       CH.sub.3 OC.sub.2 H.sub.4                         33       H          Br       C.sub.6 H.sub.13                                  34       2-CH.sub.3 H        CH.sub.3 OC.sub.3 H.sub.6                         35       2-CH.sub.3 H        CH.sub.3 OC.sub.2 H.sub.4                         36       2-CH.sub.3 H        CH.sub.3                                          37       2-CH.sub.3 H        C.sub.4 H.sub.9                                   ______________________________________                                    

                  TABLE 2                                                          ______________________________________                                          ##STR15##                                                                     Example                                                                        No.       R       X       A     B                                              ______________________________________                                         38        H       H       --    CH.sub.3                                       39        H       H       --    C.sub.4 H.sub.9                                40        H       H       O     C.sub.2 H.sub.5                                41        H       H       NH    CH.sub.3                                       42        H       H       NH    C.sub.4 H.sub.9                                43        H       H       NH    C.sub.6 H.sub.5                                44        H       CH.sub.3                                                                               --    CH.sub.3                                       45        H       CH.sub.3                                                                               --    C.sub.2 H.sub.5                                46        H       CH.sub.3                                                                               --    C.sub.4 H.sub.9                                47        H       CH.sub.3                                                                               --    i-C.sub.3 H.sub.7                              48        H       CH.sub.3                                                                               --    C.sub.6 H.sub.5                                49        H       CH.sub.3                                                                               O     C.sub.2 H.sub.5                                50        H       CH.sub.3                                                                               O     C.sub.4 H.sub.9                                51        H       CH.sub.3                                                                               NH    CH.sub.3                                       52        H       CH.sub. 3                                                                              NH    C.sub.2 H.sub.5                                53        H       CH.sub.3                                                                               NH    C.sub.3 H.sub.7                                54        H       CH.sub.3                                                                               NH    i-C.sub.3 H.sub.7                              55        H       CH.sub.3                                                                               NH    C.sub.4 H.sub.9                                56        H       CH.sub.3                                                                               NH    (CH.sub.2).sub.6Cl                             57        H       CH.sub.3                                                                               NH    CH.sub.2C.sub.6 H.sub.5                        58        H       CH.sub.3                                                                               NH    C.sub.6 H.sub.5                                59        H       CH.sub.3                                                                               NH    o-CH.sub.3C.sub.6 H.sub.4                      60        H       CH.sub.3                                                                               NH    m-CH.sub.3C.sub.6 H.sub.4                      61        H       CH.sub.3                                                                               NH    p-CH.sub.3C.sub.6 H.sub.4                      62        H       CH.sub.3                                                                               NH    m-ClC.sub.6 H.sub.4                            63        H       CH.sub.3                                                                               NH    2,4-(CH.sub.3).sub.2C.sub.6 H.sub.3            64        H       CH.sub.3                                                                               NH    i-C.sub.4 H.sub.9                              65        H       CH.sub.3                                                                               NH    CH.sub.2CHCH.sub.2                             66        H       C.sub.2 H.sub.5                                                                        --    C.sub.4 H.sub.9                                67        H       C.sub.2 H.sub.5                                                                        O     C.sub.2 H.sub.5                                68        H       C.sub.2 H.sub.5                                                                        NH    CH.sub.3                                       69        H       C.sub.2 H.sub.5                                                                        NH    C.sub.4 H.sub.9                                70        H       C.sub.2 H.sub.5                                                                        NH    C.sub.6 H.sub.5                                71        CH.sub.3                                                                               CH.sub.3                                                                               --    C.sub.4 H.sub.9                                72        CH.sub.3                                                                               CH.sub.3                                                                               O     C.sub.2 H.sub.5                                73        CH.sub.3                                                                               CH.sub. 3                                                                              NH    C.sub.4 H.sub.9                                74        CH.sub.3                                                                               CH.sub.3                                                                               NH    C.sub.6 H.sub.5                                75        H       Cl      --    CH.sub.3                                       76        H       Cl      --    C.sub.4 H.sub.9                                77        H       Cl      O     C.sub.2 H.sub.5                                78        H       Cl      NH    CH.sub.3                                       79        H       Cl      NH    C.sub.4 H.sub.9                                80        H       Cl      NH    C.sub.6 H.sub.5                                81        H       Cl      NH    CH.sub.2C.sub.6 H.sub.5                        ______________________________________                                     

We claim:
 1. A process for dyeing and printing synthetic fibre materials comprising employing therefor azo disperse dyestuffs of the formula (I) ##STR16## wherein R denotes hydrogen or C₁ -C₄ -alkyl,X denotes R, Cl or Br, m denotes the number 0 or 1, n denotes a number from 2 to 4, p denotes the number 0 or 1, A denotes oxygen or --NR-- and B denotes optionally substituted C₁ -C₈ -alkyl, alkenyl, cycloalkyl, aralkyl or aryl. 